Interfacial viscosification of aqueous acid systems utilizing sulfonated ionomers

ABSTRACT

The present invention relates to a process for the gelation (i.e. thickening) of an aqueous acid solution which includes the steps of forming a solvent system of an organic liquid or oil and a polar cosolvent, the polar cosolvent being less than about 15 weight percent of the solvent system, a viscosity of the solvent system being less than about 100 cps; dissolving a neutralized sulfonated polymer in the solvent system to form a solution, a concentration of the neutralized sulfonated polymer in the solution being about 0.01 to about 0.5 weight percent, a viscosity of the solution being less than about 200 cps; and admixing or contacting said solution with about 5 to about 500 volume percent of the aqueous acid solution, the aqueous acid solution being immiscible with the organic liquid and the polar cosolvent and neutralized sulfonated polymer transferring from the organic liquid to the aqueous acid phase, thereby causing the aqueous acid phase to thicken (i.e. interfacial viscosification).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for the viscosification of anaqueous acid solution which includes the steps of forming a solventsystem of an organic liquid or oil and a polar cosolvent, the polarcosolvent being less than about 15 weight percent of the solvent system,a viscosity of the solvent system being less than about 100 cps;dissolving a neutralized or unneutralized sulfonated polymer (waterinsoluble) in the solvent system to form a solution, a concentration ofthe neutralized sulfonated polymer in the solution being about 0.01 toabout 0.5 weight percent, a viscosity of the solution being less thanabout 200 cps; and admixing or contacting said solution with about 5 toabout 500 volume percent of the aqueous acid solution the aqueous acidsolution being immiscible with the organic liquid and the polarcosolvent and neutralized sulfonated polymer transferring from theorganic liquid to the aqueous acid phase, thereby causing the aqueousacid phase to gel.

2. Description of the Prior Art

There are many applications for very viscous or gelled solutions ofpolymers in water which are quite diverse. There are also a number ofphysical and chemical techniques for preparing such systems. The presentinvention is concerned with a process for gelling (i.e. thickening) anaqueous acid solution by contacting the aqueous acid solution with arelatively low viscosity, organic liquid solution of an ionic polymer.

The instant invention differs from a number of applications, Ser. Nos.223,482; 136,837; and 106,027, filed by Robert Lundberg et al, one ofthe instant inventors. These previously filed applications were directedto the gelling of the organic liquid by a water insoluble, neutralizedsulfonated polymer whereas the instant invention is directed to thegelling of an aqueous acid solution. Quite unexpectedly, it has beendiscovered that when the concentration of the sulfonated polymer insolution is maintained in a critical concentration range of 0.01 to 0.5weight percent of the total volume of solvent, which is a mixture ofnonpolar organic liquid and a polar cosolvent, upon the addition ofaqueous acid solution, a transfer of the polar solvent and waterinsoluble neutralized sulfonated polymer from the nonpolar organicliquid phase to the aqueous acid phase occurs. The water insolubleneutralized sulfonated polymer causes the aqueous acid phase to gel,wherein the neutralized sulfonated polymer is insoluble in the aqueousacid phase. In the previously filed patent applications, substantialviscosification of the nonpolar organic liquid phase did not occur untilthe concentration of the neutralized sulfonated polymer was sufficientlyhigh enough to permit chain entanglement of adjacent polymer moleculesthereby completely filling the solvent space. The gelation of theaqueous acid phase of the instant invention does not occur by thispreviously described mechanism because the resultant concentration ofwater insoluble, neutralized sulfonated polymer is not sufficiently highenough to permit chain entanglement. The mechanism of gelation of theaqueous acid phase, as defined in the instant invention, occurs by theformation of macroscopic spherical polymer membranes or films dispersedthroughout the aqueous acid phase, wherein large volumes of the aqueousacid are encapsulated within a series of minute polymer bags (i.e.pseudo-emulsion).

The instant invention describes a process which permits (1) thepreparation of polymer solutions of sulfonated polymers in organicliquid having reasonably low viscosities (i.e., less than about 200cps); and (2) the preparation of extremely viscous solutions or gels ofan aqueous acid from such solutions by a process of mixing or contactingan aqueous acid solution with the polymer solution. These operations areachieved by the use of the appropriate concentration; 0.01 to 0.5 weightpercent of water insoluble, neutralized sulfonated polymers, having lowconcentrations of ionic groups present, preferably metal sulfonategroups. Such polymers are described in detail in a number of U.S.Patents (U.S. Pat. Nos. 3,836,511; 3,870,841; 3,847,854; 3,642,728; and3,921,021) which are herein incorporated by reference. These polymerspossess unusual solution characteristics some of which are described inU.S. Pat. No. 3,931,021. Specifically, these polymers, such as lightlysulfonated polystyrene, containing about 2 mole percent sodium sulfonatependant to the aromatic groups, are typically not soluble in solventscommonly employed for polystyrene itself. However, the incorporation ofmodest levels of polar cosolvents permit the rapid dissolution of suchionic polymers to form homogeneous solutions of moderate viscosity.

In the instant process, the role of the polar cosolvent is that ofsolvating the ionic groups while the main body of the solvent interactswith the polymer backbone. For example, xylene is an excellent solventfor the polystyrene backbone and when combined with 5 percent methanolwill dissolve, readily and rapidly, the previous example of lightlysulfonated polystyrene.

The remarkable and surprising discovery of the instant invention is thatwhen small (or large) amounts of an aqueous acid solution are combinedand mixed with solutions of ionic polymers dissolved at lowconcentrations (0.01 to 0.5 weight percent) in such mixed solventsystems as those described above, a phase transfer of the waterinsoluble, neutralized sulfonated polymer and cosolvent occurs from thenonpolar organic liquid phase to the aqueous acid phase, wherein theaqueous acid phase gels. Indeed, it is possible to achieve increases inviscosity of the aqueous acid phase by factors of 10³ (1,000) or more bythe addition of only 5 to 15 percent aqueous acid based on the polymersolution volume. This unusual behavior is postulated to arise from theremoval of the polar cosolvent and water insoluble, neutralizedsulfonated polymer from the organic liquid phase into the separateaqueous acid phase which then gels (i.e. thickens).

SUMMARY OF THE INVENTION

The present invention relates to a process for the gelation (i.e.thickening) of an aqueous acid solution which includes the steps offorming a solvent system of an organic liquid or oil and a polarcosolvent, the polar cosolvent being less than about 15 weight percentof the solvent system, a viscosity of the solvent system being less thanabout 100 cps; dissolving a neutralized sulfonated polymer in thesolvent system to form a solution, a concentration of the neutralizedsulfonated polymer in the solution being about 0.01 to about 0.5 weightpercent, a viscosity of the solution being less than about 200 cps; andadmixing or contacting said solution with about 5 to about 500 volumepercent of the aqueous acid solution, the aqueous acid solution beingimmiscible with the organic liquid and the polar cosolvent andneutralized sulfonated polymer transferring from the organic liquid tothe aqueous acid phase, thereby causing the aqueous acid phase to gel.

Accordingly, it is a primary object of the instant invention to describean economical process for forming a highly viscous or gelled aqueousacid solution having a viscosity from approximately 50 cps to about1,000 cps.

GENERAL DESCRIPTION

The present invention relates to a process for the gelation of anaqueous acid solution which includes the steps of forming a solventsystem of an organic liquid or oil and a polar cosolvent. The polarcosolvent being less than about 15 weight percent of the solvent systemwith a viscosity of the solvent system being less than about 100 cps.Subsequently dissolving a neutralized sulfonated polymer in the solventsystem to form a solution with a concentration of the neutralizedsulfonated polymer in the solution being about 0.01 to about 0.5 weightpercent. The viscosity of the solution being less than about 200 cps.Admixing or contacting said solution with about 5 to about 500 volumepercent of the aqueous acid solution, the aqueous acid solution beingimmiscible with the organic liquid and the polar cosolvent andneutralized sulfonated polymer transferring from the organic liquid tothe aqueous acid phase, thereby causing the aqueous acid phase to gel.

The gelled or thickened aqueous acid phase having a viscosity greaterthan 50 cps is formed by the addition of an aqueous acid solution to awater insoluble solution which comprises a water insoluble, neutralizedsulfonated polymer, a nonpolar organic liquid and a polar cosolvent,wherein the solution has a viscosity less than 200 cps. Theconcentration of neutralized sulfonated polymer in the solution is 0.01to 0.5 weight percent, the polar cosolvent and water insoluble,neutralized sulfonated polymer rapidly transfers from the solution tothe aqueous acid phase which undergoes immediate gelation. The organicliquid phase can be removed from the gel by conventional liquidextraction methods. The formation of the aqueous fluid or water having aviscosity of at least 50 cps from the organic solution having aviscosity less than 200 cps, can be quite rapid in the order of lessthan 1 minute to about 24 hours, more preferably less than 1 minute toabout 30 minutes, and most preferably less than 1 minute to about 10minutes; however, this depends on temperature, shear, solvent type, etc.

The component materials of the instant process generally include a waterinsoluble, ionomeric polymer such as a water insoluble, neutralizedsulfonated polymer at a critical concentration level of 0.01 to 0.5weight percent, a nonpolar organic liquid, polar cosolvent and anaqueous acid solution.

Gelation of an aqueous acid phase does not occur, if one employs aconventional unsulfonated polymer or a water soluble, neutralizedsulfonated polymer in place of the water insoluble, neutralizedsulfonated polymer, but rather only classical phase separation occurs.

In the instant invention, the gelation of the aqueous acid phase occursby the formation of geometrically shaped spheres (so-calledpseudo-emulsion phase) of the water insoluble, neutralized sulfonatedpolymer within the aqueous acid phase, wherein the water is encapsulatedwithin these geometrically shaped spheres. During the process,approximately 10 weight percent of the nonpolar organic liquid alsotransfers to the aqueous acid phase and is encapsulated within thesegeometrically shaped spheres.

It has been additionally discovered that the addition of a nonionicsurfactant can further enhance the gelation of the aqueous acidsolution. In acidic solutions, the nonionic surfactant is not needed forstability (25° C.), however, the viscosity of these pseudo-emulsionsystems tends to increase significantly with the addition of smallamounts of the nonionic material (typically <0.04 g/l).

The nonionic surfactants which can be employed in the instant inventionare selected from the group consisting of polyethylene oxide -polypropylene oxide -block copolymer (polyols), polyoxyethylene sorbitanfatty acid esters, sorbitan fatty acid esters, fatty acids and fattyacid derivatives such as ethoxylated fatty acid-Armals (Ethofat®), amidederivatives such as Armals (Ethomid®), stearatic acid and stearatederivatives, fluorine-containing nonionic surfactants, fatty alcohols,alcohol esters, glycinol esters and polyethylene glycol esters. Typicalexamples of nonionic surfactants are BASF (Pluronics®), ICI (Atlas®) ICI(Bris®) and ICI (Arlacel®), ICI (Tween® series), 3M (Fluorad®) andShenex (Adol®), wherein polyethylene oxide - polypropylene oxide - blockcopolymer (polyols) is preferred. The nonionic surfactant is added tothe solvent system at a concentration of about 0.0001 to about 1.0weight percent of total solvent, more preferably about 0.001 to about0.5, and most preferably about 0.001 to about 0.005.

In general, the water insoluble ionomeric polymer will comprise fromabout 10 to about 200 meq. pendant ionomeric groups per 100 grams ofpolymer, more preferably from 10 to 100 meq. pendant ionomeric groups.The ionic groups may be conveniently selected from the groups consistingof carboxylate, phosphonate, and sulfonate, preferably sulfonate groups.The ionomers utilized in the instant invention are neutralized with thebasic materials selected from Groups IA, IIA, IB and IIB of the PeriodicTable of Elements and lead, tin and antimony, as well as ammonium andamine counterions. Ionic polymers which are subject to the process ofthe instant invention are illimitable and include both plastic andelastic polymers. Specific polymers include sulfonated polystyrene,sulfonated t-butyl styrene, sulfonated ethylene copolymers, sulfonatedpropylene copolymers, sulfonated styrene/acrylonitrile copolymers,sulfonated styrene/methyl methacrylate copolymers, sulfonated blockcopolymers of styrene/ethylene oxide, acrylic acid copolymers withstyrene, sulfonated polyisobutylene, sulfonated ethylene-propyleneterpolymers, sulfonated polyisoprene, and sulfonated elastomers andtheir copolymers. The preferred polymers of the instant invention areethylenepropylene terpolymers and polystyrene, wherein polystyrene ismost preferred.

Neutralization of the cited polymers with appropriate metal hydroxides,metal acetates, metal oxides, or ammonium hydroxide etc., can beconducted by means well-known in the art. For example, the sulfonationprocess as with Butyl rubber containing a small 0.3 to 1.0 mole percentunsaturation can be conducted in a suitable solvent such as toluene,with acetyl sulfate as the sulfonated agent, such as described in U.S.Pat. No. 3,836,511. The resulting sulfonic acid derivative can then beneutralized with a number of different neutralization agents such as asodium phenolate and similar metal salts. The amounts of suchneutralization agents employed will normally be equal stoichiometricallyto the amount of free acid in the polymer plus any unreacted reagentwhich is still present. It is preferred that the amount of neutralizingagent be equal to the molar amount of sulfonating agent originallyemployed plus 10 percent more to insure full neutralization. The use ofmore of such neutralization agent is not critical. Sufficientneutralization agent is necessary to effect at least 50 percentneutralization of the sulfonic acid groups present in the polymer,preferably at least 90 percent, and most preferably essentially completeneutralization of such acid groups should be effected.

The degree of neutralization of said ionomeric groups may vary from 0(free acid form) to 100 mole percent, preferably 50 to 100 percent. Withthe utilization of neutralized ionomers in this instant invention, it ispreferred that the degree of neutralization be substantially complete,that is with no substantial free acid present and without substantialexcess of the base other than that needed to insure neutralization. Theneutralized ionomers possess greater thermal stability compared to itsacid form. Thus, it is clear that the polymers which are normallyutilized in the instant invention comprise substantially neutralizedpendant groups, and in fact, an excess of the neutralizing material maybe utilized without defeating the objects of the instant invention.

The ionomeric polymers of the instant invention may vary in numberaverage molecular weight from 1,000 to 10,000,000 preferably from 5,000to 500,000, most preferably from 10,000 to 200,000. These polymers maybe prepared by methods known in the art, for example, see U.S. Pat. No.3,642,728, hereby incorporated by reference.

The preferred ionic copolymers for use in the instant invention, e.g.,sulfonated polystyrene and substituted derivatives thereof, may beprepared by the procedures described in U.S. Pat. No. 3,870,841, filedOct. 2, 1972, in the names of H. S. Makowski, R. D. Lundberg and G. H.Singhal, hereby incorporated by reference.

The water insoluble, ionomeric polymers may be incorporated into theorganic liquid at a level of from 0.1 to 0.5 weight percent and morepreferably from 0.01 to 0.4 weight percent, based on the organic liquidand the polar cosolvent.

Specific examples of preferred ionomeric polymers which are useful inthe instant invention include sulfonated polystyrene, sulfonatedpoly-t-butyl styrene, sulfonated polyethylene (substantiallynoncrystalline), and sulfonated ethylene copolymers, sulfonatedpolypropylene (substantially noncrystalline), and sulfonatedpolypropylene copolymers, sulfonated styrene methyl methacrylatecopolymers, (styrene)-acrylic acid copolymers, sulfonatedpolyisobutylene, sulfonated ethylene-propylene terpolymers, sulfonatedpolyisoprene, sulfonated polyvinyl toluene and sulfonated polyvinyltoluene copolymers.

The ionomeric polymers of the instant invention may be prepared prior toincorporation into the organic solvent, or by neutralization of the acidfrom a situ. For example, preferably the acid derivative is neutralizedimmediately after preparation. For example, if the sulfonation ofpolystyrene is conducted in solution, then the neutralization of thatacid derivative can be conducted immediately following the sulfonationprocedure. The neutralized polymer may then be isolated by meanswell-known to those skilled in the art, i.e., coagulation, steamstripping, or solvent evaporation, because the neutralized polymer hassufficient thermal stability to be dried for employment at a later timein the process of the instant invention. It is well-known that theunneutralized sulfonic acid derivatives do not possess good thermalstability and the above operations avoid that problem.

It is also possible to neutralize the acid form of these polymers insitu; however, this is not a preferred operation, since in situneutralization requires preparation of the sulfonic acid in the organicliquid which is to be subjected to the instant process, or the acid formof the ionic polymer must be dissolved in said organic liquid. Thelatter approach may involve handling of an acid form of an ionic polymerwhich has limited thermal stability. Therefore, it is quite apparentthat the preparation and isolation of a neutralized ionic polymeraffords the maximum latitude in formulation, less problems in handlingpolymers of limited thermal stability and maximum control over the finalmixture of ionic polymer, polar cosolvent and organic liquid.

The organic liquids, which may be utilized in the instant invention, areselected with relation to the ionic polymer and vice-versa. The organicliquid is selected from the group consisting essentially of aromatichydrocarbons, cyclic aliphatic ethers, aliphatic ethers, or organicaliphatic esters and mixtures thereof.

Specific examples of organic liquids to be employed with the varioustypes of polymers are:

    ______________________________________                                        Polymer           Organic Liquid                                              ______________________________________                                        sulfonated polystyrene                                                                          benzene, toluene, ethyl                                                       benzene, methylethyl                                                          ketone, xylene, styrene,                                                      ethylene dichloride,                                                          methylene chloride.                                         sulfonated poly-t-butyl-                                                                        benzene, toluene, xylene,                                   styrene           ethyl benzene, styrene,                                                       t-butyl styrene, aliphatic                                                    oils, aromatic oils, hexane,                                                  heptane, decane, nonane.                                    sulfonated ethylene-                                                                            pentane, aliphatic and                                      propylene terpolymer                                                                            aromatic solvents, oils                                                       such as Solvent "100                                                          Neutral", "150 Neutral"                                                       and similar oils, benzene,                                                    diesel oil, toluene,                                                          xylene, ethyl benzene,                                                        pentane, hexane, heptane,                                                     octane, isooctane, nonane,                                                    decane aromatic solvents,                                                     ketone solvents.                                            sulfonated styrene-methyl-                                                                      dioxane, halogenated ali-                                   methacrylate copolymer                                                                          phatics, e.g., methylene                                                      chloride, tetrahydrofuran.                                  sulfonated polyisobutylene                                                                      saturated aliphatic hydro-                                                    carbons, diisobutylene,                                                       triisobutylene, aromatic                                                      and alkyl substituted                                                         aromatic hydrocarbons,                                                        chlorinated hydrocarbons,                                                     n-butyl ether, n-amyl                                                         ether, methyl oleate,                                                         aliphatic oils, oils pre-                                                     dominantly paraffinic                                                         in nature and mixtures                                                        containing naphthenic                                                         hydrocarbons. "Solvent 100                                                    Neutral", "Solvent 150                                                        Neutral" and all related                                                      oils, low molecular weight                                                    polymeric oils such as                                                        squalene, white oils and                                                      process oils having 60                                                        percent or less aromatic                                                      content.                                                    sulfonated polyvinyl                                                                            toluene, benzene, xylene,                                   toluene           cyclohexane, ethyl benzene,                                                   styrene, methylene chlo-                                                      ride, ethylene dichloride.                                  ______________________________________                                    

The method of the instant invention includes incorporating a polarcosolvent, for example, a polar cosolvent in the mixture of organicliquid and water insoluble ionomer to solubilize the pendant ionomericgroups. The polar cosolvent will have a solubility parameter of at least10.0, more preferably at least 11.0 and is water miscible and maycomprise from 0.1 to 15.0 weight percent, preferably 0.1 to 5.0 weightpercent of the total mixture of organic liquid, water insolubleionomeric polymer, and polar cosolvent. The solvent system of polarcosolvent and organic liquid in which the water insoluble, neutralizedsulfonated polymer is dissolved contains less than about 10.0 weightpercent of the polar cosolvent, more preferably about 0.1 to about 5weight percent, and most preferably about 1.0 to about 5.0 weightpercent. The viscosity of the solvent system is less than about 1,000cps, more preferably less than about 800 cps and most preferably lessthan about 500 cps.

Normally, the polar cosolvent will be a liquid at room temperature;however, this is not a requirement. It is preferred, but not required,that the polar cosolvent be soluble or miscible with the organic liquidat the levels employed in this invention. The polar cosolvent isselected from the group consisting essentially of water solublealcohols, amines, di- or trifunctional alcohols, amides, acetamides,phosphates, or lactones and mixtures thereof. Especially preferred polarcosolvents are aliphatic alcohols such as methanol, ethanol, n-propanol,isopropanol, 1,2-propane diol, monoethyl ether of ethylene glycol, andn-ethylformamide.

The amount of aqueous acid solution added to the solution of waterinsoluble, neutralized sulfonated polymer, organic liquid and polarcosolvent having a viscosity of less than about 200 cps, is about 5 toabout 500 volume percent of water, more preferably about 10 to about 300volume percent water, most preferably about 10 to about 200 volumepercent water.

The aqueous acid solution of hydrochloric acid, in which the waterinsoluble neutralized sulfonated polymer thickens, contains less thanabout 40 weight percent acid, more preferably about 0.1 to about 30weight percent, and most preferably about 1.0 to about 20 weightpercent.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The following examples will demonstrate the performance of sulfonatedpolystyrene of varying sulfonate levels in several specific aqueousenvironments.

Example I

Table I shows the effectiveness of 6.05 mole percent sulfonatedpolystyrene as a viscosifier for a 10 percent hydrochloric acidsolution. The data indicate that acid solutions containingpseudo-emulsion particles can be used to significantly enhance theviscosity of the aqueous acid phase even though the sulfonated polymeris hydrocarbon soluble. The viscosity of the hydrocarbon solventcontaining the sulfonated polymer is less than 100 centipoise. The dataalso show that the pseudo-emulsion phase can be produced over a widerange of "dilution" with little change in viscosity. Each individualsphere is capable of expanding to accommodate the increased aqueous acidphase volume by absorption through the polymer membrane. The size ofeach sphere increases, but the volume fraction of spheres remainsconstant. The constancy of the viscosity confirms this fact.

                  TABLE I                                                         ______________________________________                                        VISCOSITY (30 RPM) OF PSEUDO-EMULSION*                                        VERSUS VOLUME OF HCl SOLUTION (10%)                                           Solution Volume (ml)**                                                                          Viscosity (cps)                                             ______________________________________                                        25                696                                                         30                500                                                         35                384                                                         40                544                                                         45                592                                                         ______________________________________                                         *Initial solution concentrations: 15 ml. at 0.5 g/l of 6.05 mole %            sulfopolystyrene.                                                             **Amount of acid solution used to prepare pseudoemulsion phase.          

Example II

Table 2 shows the effectiveness of utilizing a nonionic surfactant (BASFPluronic® F-108) at very low concentrations in the preparation ofpseudo-emulsions in 10 weight percent acid solution. The sulfonatedpolystyrene was initially dissolved in a xylene/methanol solvent system.The data indicates that these acid solutions containing pseudo-emulsionparticles in conjugation with minute amounts of nonionic surfactant canbe used to significantly enhance the viscosity of the aqueous acidsolution even though the polymer is wholly hydrocarbon soluble.Moreover, the data shows that the surfactant produces marked enhancedviscosity over that observed without surfactant present (Table 1). Thedata also shows that these pseudo-emulsion systems can be produced overa wide range of "dilution" with relatively minor modification inviscosity.

                  TABLE 2                                                         ______________________________________                                        VISCOSITY (12 RPM) OF PSEUDO-EMULSION (NaSPS)                                 VERSUS VOLUME OF HCl SOLUTION                                                 (0.04 g/l NONIONIC SURFACTANT)                                                Solution Volume (ml.)*                                                                          Viscosity (cps)                                             ______________________________________                                        25                5,831                                                       35                4,582                                                       45                5,831                                                       ______________________________________                                         *Amount of acid solution used to prepare pseudoemulsion phase.                Concentration of acid is 10.0 weight percent.                            

What is claimed is:
 1. A process for forming a thickened aqueous acidfluid, said solution having a viscosity of at least about 50 cps whichincludes the steps of:(a) forming a solvent system of an organic liquidand a polar cosolvent, said polar cosolvent being less than about 15weight percent of said solvent system, a viscosity of said solventsystem being less than about 1,000 cps; (b) dissolving a waterinsoluble, free acid, or neutralized sulfonated polymer in said solventsystem to form a polymeric solution, a concentration of saidunneutralized or neutralized sulfonated polymer in said solution beingabout 0.01 to less than 0.4 weight percent, a viscosity of said solutionbeing less than about 200 cps; and (c) adding about 5 to about 500volume percent aqueous acid solution to said polymeric solution, saidaqueous acid solution being immiscible with said polymeric solution,with said polar cosolvent and said water insoluble, neutralizedsulfonated polymer transferring from said polymeric solution to saidaqueous acid solution causing the viscosity of said aqueous acidsolution to increase to at least 50 cps.
 2. A process according to claim1 further including a means for removing said organic liquid from saidfluid of said aqueous acid solution.
 3. A process according to claim 1,wherein said unneutralized or neutralized sulfonated polymer has about10 (free acid) to about 200 meq. of pendant SO₃ H groups per 100 gramsof polymer.
 4. A process according to claim 3 wherein said SO₃ H groupsare neutralized within an ammonium or metal counterion.
 5. A processaccording to claim 4 wherein said metal counterion is selected from thegroup including antimony, tin, lead or Groups IA, IIA, IB or IIB of thePeriodic Table of Elements.
 6. A process according to claim 4 whereinsaid SO₃ H groups are at least 90 mole percent neutralized.
 7. A processaccording to claim 1 wherein said neutralized sulfonated polymer isformed from an elastomeric polymer.
 8. A process according to claim 7wherein said elastomeric polymer is selected from the group includingEPDM terpolymer or Butyl rubber.
 9. A process according to claim 1wherein said neutralized sulfonated polymer is formed from athermoplastic.
 10. A process according to claim 9 wherein saidthermoplastic is selected from the group including polystyrene, t-butylstyrene, ethylene copolymers, propylene copolymers, orstyrene/acrylonitrile copolymers.
 11. A process according to claim 1wherein said polar cosolvent has a greater polarity than said organicliquid.
 12. A process according to claim 1 wherein said polar cosolventis selected from the group including aliphatic alcohols, aliphaticamines, di- or trifunctional aliphatic alcohols, water miscible amides,acetamides, phosphates, or lactones and mixtures thereof.
 13. A processaccording to claim 1 wherein said polar cosolvent is selected from thegroup including methanol, ethanol, propanol, isopropanol and mixturesthereof.
 14. A process according to claim 1 wherein said polar cosolventhas a solubility parameter of at least about 10 and is water miscible.15. A process according to claim 1 wherein said organic liquid isselected from the group consisting of aromatic hydrocarbons, chlorinatedaliphatic hydrocarbons, aliphatic hydrocarbons and mixtures thereof. 16.A process according to claim 1 wherein said organic liquid is selectedfrom the group including aliphatic hydrocarbons or aromatichydrocarbons.
 17. A process according to claim 1 wherein said organicliquid is selected from the group including benzene, toluene, ethylbenzene, xylene or styrene and mixtures thereof.
 18. A process accordingto claim 17 wherein said neutralized sulfonated polymer is formed frompolystyrene.
 19. The product prepared by the process of claim 1.